WO2014019992A1 - Procédé de production assistée par le vide d'un élément en mousse pur/pir - Google Patents

Procédé de production assistée par le vide d'un élément en mousse pur/pir Download PDF

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Publication number
WO2014019992A1
WO2014019992A1 PCT/EP2013/065922 EP2013065922W WO2014019992A1 WO 2014019992 A1 WO2014019992 A1 WO 2014019992A1 EP 2013065922 W EP2013065922 W EP 2013065922W WO 2014019992 A1 WO2014019992 A1 WO 2014019992A1
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WO
WIPO (PCT)
Prior art keywords
mold
reaction mixture
negative pressure
pur
pir
Prior art date
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PCT/EP2013/065922
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German (de)
English (en)
Inventor
Reinhard Albers
Patrick KLASEN
Stephanie Vogel
Original Assignee
Bayer Materialscience Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Materialscience Ag filed Critical Bayer Materialscience Ag
Priority to CN201380040779.3A priority Critical patent/CN104507656A/zh
Priority to US14/418,251 priority patent/US9950454B2/en
Priority to EP13741794.5A priority patent/EP2879852B1/fr
Priority to MX2015001328A priority patent/MX361996B/es
Publication of WO2014019992A1 publication Critical patent/WO2014019992A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3403—Foaming under special conditions, e.g. in sub-atmospheric pressure, in or on a liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
    • B29C44/0415—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities by regulating the pressure of the material during or after filling of the mould, e.g. by local venting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1209—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements by impregnating a preformed part, e.g. a porous lining
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing

Definitions

  • the present invention relates to a process for producing a PUR / PIR foam body, comprising the steps of providing a mold adapted to apply a negative pressure to the interior of the mold; charging a reaction mixture comprising an isocyanate-reactive composition A and an isocyanate B into the mold and applying a negative pressure to the interior of the mold such that the negative pressure acts on the charged reaction mixture.
  • the present invention therefore has the task of providing such a method.
  • the process according to the invention is a discontinuous process in which a negative pressure acts on a polyurethane / polyisocyanurate reaction mixture (PUR / PIR reaction mixture). This takes place in an evacuable form.
  • the mold can be a foam mold in the sense that the reaction mixture enters the foam mold as such is introduced and after removal from the mold a foam body corresponding foam is obtained (foam mold with evacuable cavity).
  • the mold represents an evacuation cabin, so that, for example, the actual foam mold is introduced into this cabin, is filled with the reaction mixture, the mold is closed and then the negative pressure can be applied.
  • the setting time is measured manually, for example, by repeatedly dipping a wooden stick into the reaction mixture that has already been distended and withdrawing it again, and determining when the rod pulls threads.
  • the time measurement begins with the mixing of the reaction mixture.
  • tF mold filling time: completion of filling of the mold by the foamed reaction mixture.
  • the index (index) of the reaction mixture is defined as the molar ratio of NCO groups to NCO-reactive groups multiplied by 100.
  • the index is 320 320, more preferably 340 340.
  • Foams containing urethane and isocyanurate groups can be used in particular as starting components: Compounds having at least two isocyanate-reactive hydrogen atoms having a molecular weight in the range from 400 g / mol to 10000 g / mol, for example amino groups, thiol groups, hydroxyl groups or carboxyl-containing compounds a
  • polymeric MDI polymeric MDI
  • Caibodiimid phenomenon urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret polyisocyanates, particularly preferably on the basis of Polyphenylpolymethylenpolyisocyanat
  • blowing agents in A are fluorinated hydrocarbons (HFC), fluorinated olefins (HFO), hydrocarbons and mixtures thereof.
  • the isocyanate-reactive composition comprises: (i) an aromatic polyester polyol A1 having a hydroxyl number of 100 100 mg KOH / g to ⁇ 350 mg KOH / g, an average OH functionality of 1,8 1.8 to ⁇ 6.5,
  • an aliphatic polyether polyol A2a having a hydroxyl value of ⁇ 110 mg KOH / g to ⁇ 500 mg KOH / g, an average OH functionality of ⁇ 1.5 to ⁇ 5.5
  • another aliphatic polyether polyol A2b having a hydroxyl number of ⁇ 15 mg KOH / g to ⁇ 150 mg KOH / g, an average OH functionality of ⁇ 1.5 to ⁇ 5.5 and an ethylene oxide content of ⁇ 0 mass% to ⁇ 50 mass%, based on the Total mass of A2b
  • a blowing agent component A3 (iii) a blowing agent component A3; and (iv) a catalyst component A4 comprising a catalyst A4a for catalysing polyurethane formation and a catalyst A4b for catalysing polyisocyanurate formation.
  • polyester polyols A1a are polycondensates of di- and also tri- and tetraols and di- as well as tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
  • the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols can be used to prepare the polyesters become.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester.
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate. Preference graze ethylene glycol and diethylene glycol used
  • polycarboxylic acids examples include succinic acid, fumaric acid, maleic acid, maleic anhydride, glutaric acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid or the like Adipic acid and phthalic anhydride used
  • the aromatic polyester polyol A1a has a hydroxyl value of ⁇ 150 mg KOH / g to ⁇ 340 mg KOH / g (more preferably ⁇ 200 mg KOH / g to ⁇ 340 mg KOH / g) and a peak OH functionality of ⁇
  • the acid number is preferably in the range of 0,1 0.1 mg KOH / g to ⁇ 5.0 mg KOH / g.
  • Useful aliphatic polyether polyols A2a are, for example, polytetramethylene glycol polyethers obtainable by polymerization of tetrahydrofuran by means of cationic ring opening.
  • polyether polyols are addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to di- or polyfunctional starter molecules.
  • Suitable starter molecules are, for example, water, ethylene glycol, diethylene glycol, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, pentaerythritol, sorbitol, sucrose, ethylenediamine, toluenediamine, triethanolamine, 1,4-butanediol, 1,6-hexanediol and low molecular weight, hydroxyl-containing esters such polyols with dicarboxylic acids It is preferred that the aliphatic polyether polyol A2a has a hydroxyl value of ⁇ 200 mg KOH / g to ⁇ 500 mg KOH / g (more preferably 220 220 mg KOH / g to ⁇ 450 mg KOH / g) and average OH functionality of 1 1 , 8 to 3.5.
  • hydroxyl numbers selected make it possible to characterize the aliphatic polyetherpolyol A2a as a comparatively short-chain polyol.
  • a preferred aliphatic polyether polyol A2a is furthermore obtained from the reaction of one or more sugar-containing starter molecules with propylene oxide.
  • the aliphatic polyether polyol A2b basically the same starting materials as for the polyether polyol A2a can be used. It is preferred that this polyether polyol A2b has a hydroxyl value of 20 20 mg KOH / g to ⁇ 120 mg KOH / g (more preferably 25 mg KOH / g to ⁇ 145 mg KOH / g) and average OH functionality of 1,8 1.8 bis ⁇ 3.5. Furthermore, the ethylene oxide content of this polyol is preferably ⁇ 0% by mass to ⁇ 40, based on the total mass of A2b.
  • hydroxyl numbers selected make it possible to characterize the aliphatic polyether polyol A2b as a comparatively long-chain polyol.
  • a preferred further aliphatic polyether polyol A2b is obtained from the two-stage reaction of one or more sugar-containing and / or glycol starter molecules with ethylene oxide and propylene oxide.
  • Examples of a suitable isocyanate component B are 1,4-butylene diisocyanate, 1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 1,5- Naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and / or higher homologs (polymeric MDI), 1,3- and / or 1,4-bis- (2
  • the isocyanate is a prepolymer obtainable by reaction of an isocyanate having an NCO functionality of 2 2 and polyols having a molecular weight of 62 62 g / mol to ⁇ 8000 g / mol and OH functionalities of 1 1 , 5 to 6.
  • the blowing agent component A3 includes, for example, chemical blowing agents such as water and / or physical blowing agents such as hydrocarbon blowing agents (especially n-pentane, i-pentane and cyclopentane and mixtures thereof), halogenated hydrocarbon blowing agents and halogenated olefins.
  • examples of the polyurethane catalyst A4a are amine catalysts, in particular selected from the group triemylenediamine, N, N-dimethylcyclohexylamine, dicyclohexylmemylamine, tetramethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, triemylamine, tributylamine, dimethylbenzylamine, N, N ', N Tris (dimethylamino-propyl) hexahydiotriazine, tris (dimethylammopiopropyl) amine, tris (dimethylaminomethyl) phenol, dimethylammopropylformamide, ⁇ , ⁇ , ⁇ ', ⁇ '-
  • Tetramethylenediamine N, N, N ', N'-tetramethylbutanediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, tetramethyldiaminoethylether, dimethylpiperazine, 1,2-dimemylimidazole, 1-azabicyclo [3.3.0] octane, bis (dimethylaminopropyl) -urea, N- Methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, triethanolamine, diethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and / or dimethylethanolamine.
  • polyisocyanurate catalyst A4b examples include tin compounds such as tin (n) acetate, tin (n) octoate, tin (n) ethyl hexoate, tin (n) laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and / or dioctyltin diacetate, furthermore, nitrogen heterocycles such as tris (N, N-dimethylammopropyl) -s-hexahydrotriazine, hydroxides such as tetramethylammonium hydroxide and / or sodium hydroxide or carboxylic acid salts of an alkali metal such as sodium N - [(2-hydroxy-5-nonylphenyl) methyl] -N-methylaminoacetate, Sodium acetate, sodium octoate, potassium acetate and / or potassium octoate or mixture
  • the isocyanate-reactive composition A may further comprise auxiliaries and additives, for example: (V) at least one foam stabilizer, preferably a polyether siloxane, which is generally constructed as a copolymer of ethylene and / or propylene oxide and connected to a Polydimethylsiloxanrest, and
  • At least one flame retardant preferably brominated and / or chlorinated polyols or phosphorus compounds (such flame retardants are described, for example, in the "Kunststoffhandbuch", Volume 7 "Polyurethanes", Chapter 6.1, for example the esters of orthophosphoric acid and metaphosphoric acid, which are also halogens may be preferred at room temperature liquid
  • the catalyst component comprises a tertiary amine and a carboxylic acid salt of an alkali metal. This is preferably N, N-dimethylbenzylamine and potassium acetate
  • the mass ratio of A1: (A2a + A2b) is between ⁇ 1: 1 and ⁇ 6: 1, and the mass fraction of the sum of A1 and (A2a + A2b) is between ⁇ 65 mass% and ⁇ 85 mass%. %, based on the total mass of A.
  • Preferred is a mass ratio of ⁇ 1.5: 1 to ⁇ 4: 1 between A1: (A2a + A2b).
  • the mass ratio of A2a: A2b is between 0,3 0.3: 1 and ⁇ 3: 1.
  • a mass ratio of 0,5 0.5: 1 to ⁇ 2: 1 is preferred.
  • the isocyanate component B comprises at least one isocyanate selected from the group: 2,2'-methylenediphenyl diisocyanate, 2,4'-methylenediphenyl diisocyanate, 4,4'-methylenediphenyl diisocyanate, polynuclear methylenediphenyl diisocyanate, 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate, diisocyanatobenzene and / or naphthyl diisocyanate; and / or the isocyanate component B comprises: at least one NCO-terminated prepolymer obtainable by reaction of at least one of the abovementioned isocyanates with at least one polyol.
  • polynuclear (polymeric) MDI is preferred.
  • the polyols are preferably selected from aliphatic or aromatic polyether polyols having in each case 1 to 6 hydroxyl groups or aliphatic or aromatic polyester polyols each having a number-average molecular weight between 60 60 g / mol and ⁇ 1000 g / mol.
  • the negative pressure is already applied before tA and ⁇ 50% to ⁇ 80% of the total duration of application of the negative pressure is before tA. Because the negative pressure is already applied correspondingly before setting, the rising of a viscous reaction mixture in a mold can be further assisted. Preferably, ⁇ 55% to ⁇ 70% of the total duration of application of the negative pressure is before tA. Thus, ⁇ 20% to ⁇ 50%, preferably ⁇ 30% to ⁇ 45% of the total duration of application of the negative pressure after tA.
  • the application of the negative pressure is ended before tF.
  • the foaming reaction mixture can reach hard to reach places.
  • application of the negative pressure is completed for ⁇ 1 second to ⁇ 10 seconds, more preferably ⁇ 2 seconds to ⁇ 5 seconds, and the interior of the mold is brought to ambient pressure.
  • the application of the negative pressure to the line point is terminated by tF or after tF.
  • the characteristic number of the reaction mixture is 300 300 to ⁇ 500.
  • the characteristic number is preferably 320 320 to ⁇ 450, more preferably 340 340 to ⁇ 400.
  • the negative pressure is applied for a total duration of 5 5 seconds to ⁇ 180 seconds.
  • this duration is 10 10 seconds to ⁇ 150 seconds, more preferably 15 15 seconds to ⁇ 120 seconds.
  • the negative pressure is 0.01 0.01 bar to ⁇ 0.95 bar. This is the absolute negative pressure in the form to understand (ie no difference to an ambient pressure).
  • the negative pressure is preferably 0.1 0.1 bar to ⁇ 0.85 bar, more preferably 0.5 0.5 bar to ⁇ 0.95 bar.
  • the height of the applied negative pressure is variable over time. The negative pressure may increase and / or decrease depending on the time. For example, the negative pressure may fall from an initial value to a final value. It is also possible, for example, for the negative pressure to remain at a certain plateau value before it is lowered further to a final value. It is also possible that the negative pressure in the meantime or at the end of the application of the negative pressure decreases again (ie, the absolute pressure in the mold increases again).
  • the filling of the reaction mixture into the mold is carried out in such a way that the reaction mixture contacts at least one article in the mold and different from the mold.
  • the mold takes on the task of an evacuation chamber: the article is placed, for example, in the mold, contacted with the reaction mixture (filled), the mold is closed and the vacuum is then applied to the interior of the mold
  • the article is a hollow body and the reaction mixture is in the interior of the hollow body.
  • the reaction mixture is present between two cover layers.
  • the cover layers may be provided spaced apart by spacers or suitable receivers in the mold and the reaction mixture is then introduced between the cover layers, the mold is closed and the vacuum applied.
  • Suitable coverstock materials include, for example, plastics, steel and aluminum layers.
  • reaction mixture is present on the outside of a pipeline.
  • Such pipelines can be used, for example, as remote heating pipes.
  • the reaction mixture is present between the outside of a first pipeline and the inside of a second pipeline, wherein the first pipeline is arranged inside the second pipeline.
  • the flow index of the reaction mixture after the application of the reduced pressure is 1.0 1.0 to 1.3 1.3.
  • the flow index is defined as hE / hG, where hE is the final height of the foam and hG is the height of the foam to the gel point tG in a vacuum hard foam riser.
  • the gel point tG can be equated here with the time of the beginning of setting (see above).
  • a preferred range for the flow index is ⁇ 1.0 to ⁇ 1.2.
  • the present invention also relates to a PUR / PIR foam body obtained by a method according to the invention.
  • the PUR / PIR foam body is an insulation panel or an insulated pipe.
  • the 2-component formulation was processed with a polyol formulation A, a physical blowing agent T and an isocyanate B via the conventional mixing of these components via a laboratory scale stirrer. Furthermore, tests were carried out on a conventional high-pressure machine for processing polyurethane.
  • Polyol 1 polyester polyol having a hydroxyl number of 240 mg KOH / g, a theoretical functionality of 2.0 and a viscosity of 15600 mPas at 25 ° C. (BMS AG)
  • Polyol 2 Polyether polyol having a hydroxyl number of 440 mg KOH / g, a theoretical functionality of 2.8 and a viscosity of 440 mPas at 25 ° C. (BMS AG)
  • Polyol 3 Polyether polyol having a hydroxyl number of 28 mg KOH / g, a theoretical functionality of 2.0 and a viscosity of 860 mPas at 25 ° C. (BMS AG)
  • TEP triethyl phosphate
  • Tegostab B 8461 foam stabilizer (Evonik)
  • Desmorapid DB Catalyst (BMS AG)
  • Cyclopentane physical blowing agent (Exxon Mobil)
  • Isocyanate polymeric MDI (Desmodur 44V20L, BMS AG)
  • Example group 1 Preparation of PUR / PIR foams in the laboratory
  • the polyol formulation A was mixed with the blowing agent T and the isocyanate B in the laboratory manually via a standard stirring tool at 1000 rev / min in a reaction vessel (paper cup) and reacted.
  • the raw material temperatures were each at 23 ° C. a) Freischaumes
  • the reaction vessel was after stirring with a normalized for this method amount of the reaction mixture (265 g) in a heatable riser (V-HSR, vacuum rigid foam riser) with the height of 150 cm and the inner diameter of 9.1 cm
  • the temperature of the riser was 35 ° C.
  • the applied vacuum was 40 mbar.
  • the rise height and the pressure were detected as a function of time.
  • the following variables are to be distinguished: tG (gel point, in s), hG (height at time tG, in cm), hE (final end height of the foam, in cm), flow index ( Quotient of hE and hG).
  • Example No. VI is a comparative example.
  • Comparative Example VI differs from that of Example 2 only in the index.
  • the catalysis and the amount of blowing agent were adjusted because of the increased amount of isocyanate.
  • comparable free bulk densities and reactivity profiles are obtained, which can be recognized by reference to lay times and setting times.
  • fundamentally different are, for example, the fire properties, so VI in the free foam with the lower index has a flame height of 144 mm, whereas the flame height in the free foam of Example 2 with the higher index is already only 128 mm. This trend is also evident in molded foams, where nearly 20 mm difference in flame height was measured between the index 200 and index 350 foams. This shows the advantage of having a higher index with regard to the fire properties of PUR / PIR rigid foams.
  • Example Group 2 Mechanical Production of PUR / PIR Foams
  • a high-pressure machine HK270E (Hennecke) with an MQ-18 mixing head (Hennecke) was used.
  • the cycle pressure and the processing pressure at the mixing head were 150 bar for both raw materials.
  • the raw material temperature at the mixing head was in each case at 28 ° C.
  • the processing was carried out with a discharge rate of 391 g / s and a throttle position of 14 mm as mold was an L-shaped, lockable mold with a volume of 36.25 L, which could be operated both at atmospheric pressure and applied negative pressure.
  • the temperature of the L-form was in each case SS ° C.
  • the PUR / PIR reactant mixture first foamed against the prevailing air pressure.
  • a negative pressure 0.1 bar, 0.2 bar
  • a defined period of time 45 s, 30 s and 15 s
  • the specified bulk densities were determined on a 1000 cm 3 cube (10 ⁇ 10 ⁇ 10 cm) by determination of the corresponding mass. Further test methods were the torsion test for determining the softening point (DIN EN ISO 6721-2) and the fire test (DIN EN ISO 11925 -2). With the formulation of Example 2, tests were carried out for foam foaming with and without negative pressure on the machine. The results are summarized in Table 2 below
  • the indication of the relative negative pressure is to be understood so that, for example, a relative negative pressure of 0.1 bar corresponds to a pressure which is lower by 0.1 bar than the ambient pressure (atmospheric pressure).
  • a relative negative pressure of 0.1 bar corresponds to a pressure which is lower by 0.1 bar than the ambient pressure (atmospheric pressure).
  • the same amount of the reaction mixture was introduced into the mold, but the foaming was carried out without negative pressure.
  • the mold was only filled to 88.5%. This is due to the poor flow properties of this formulation from Example 2 with an index of 350 attributed.
  • Examples 2b, 2c and 2d foamed for 45 s, 30 s and 15 s, respectively, against a counterpressure reduced by 0.1 bar compared to Example 2a. From Table 2 it becomes clear that the choice of the right time to apply the negative pressure is decisive for the successful foaming of the mold. Thus, with Example 2d, the largest volume of the mold could be at a negative pressure of only 0.1 bar are foamed. Lowering the backpressure by a further 0.1 bar from 45 s to 60 s resulted in the case of example 2e for the 99.5% filling of the mold. Thus, in Example 2e, the optimum process conditions were found with which one and the same mold could be successfully completely filled with the formulation of Example 2 which had poor flow under normal pressure. Photographs of the foams 2e and 2a (comparison) are shown in FIG. 1, photographs of the foams 2d, 2c and 2b are shown in FIG. 2 shown.
  • the present invention therefore describes a technical process by means of which it is also possible to successfully process PUR / PIR rigid foam formulations having poor flow properties in foam-formers. This requires no adjustments to the actual chemical composition.
  • the technical processing requires only the creation of a defined negative pressure at the right time.
  • the PUR / PIR formulations with high characteristic numbers which are to be preferred on account of their better mechanical properties and their better fire behavior open up for the first time for the discontinuous production of molded foams.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé de production d'un élément en mousse PUR/PIR, comprenant les étapes consistant : à préparer un moule mis au point pour qu'une dépression soit appliquée à l'intérieur du moule ; à remplir le moule avec un mélange réactionnel contenant une composition A réagissant à l'isocyanate et une composition B isocyanate ; et à appliquer une dépression à l'intérieur du moule, de sorte que la dépression agisse sur le mélange réactionnel dont est rempli le moule. La dépression est appliquée à l'intérieur du moule au plus tard après le début de la liaison du mélange réactionnel dans le moule, et l'indice du mélange réactionnel est ≥ 300.
PCT/EP2013/065922 2012-07-31 2013-07-29 Procédé de production assistée par le vide d'un élément en mousse pur/pir WO2014019992A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201380040779.3A CN104507656A (zh) 2012-07-31 2013-07-29 真空辅助制备pur/pir泡沫体的方法
US14/418,251 US9950454B2 (en) 2012-07-31 2013-07-29 Method for the vacuum-assisted production of a PUR/PIR foam body
EP13741794.5A EP2879852B1 (fr) 2012-07-31 2013-07-29 Procédé de fabrication sous vide d'un corps de moussage pur/pir
MX2015001328A MX361996B (es) 2012-07-31 2013-07-29 Procedimiento de producción asistida por vacío de un cuerpo de espuma de pur/pir.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12178583.6A EP2692501A1 (fr) 2012-07-31 2012-07-31 Procédé de fabrication sous vide d'un corps de moussage PUR/PIR
EP12178583.6 2012-07-31

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WO2014019992A1 true WO2014019992A1 (fr) 2014-02-06

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US (1) US9950454B2 (fr)
EP (2) EP2692501A1 (fr)
CN (1) CN104507656A (fr)
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CN105280866B (zh) * 2015-09-14 2018-03-09 浙江清优材料科技有限公司 一种耐高温锂电池隔膜及其制备方法

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WO2000039497A1 (fr) 1998-12-28 2000-07-06 Shell Internationale Research Maatschappij B.V. Conduites preisolees et leur procede de production
US6627018B1 (en) * 2000-10-17 2003-09-30 Advance Usa, Llc System and method of forming composite structures
DE102009044515A1 (de) * 2008-11-18 2010-05-20 General Electric Co. Membranstruktur für vakuum-unterstütztes Formen faserverstärkten Gegenstandes
US20110260351A1 (en) * 2009-02-20 2011-10-27 Crios S.P.A. Vacuum-assisted foaming method and apparatus for moulding insulation of refrigeration containers
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DE10258546B4 (de) * 2002-12-14 2005-03-10 Stankiewicz Gmbh Verfahren und Vorrichtung zur Herstellung geschäumter Polyurethan-Formkörper
KR20140043830A (ko) * 2005-11-14 2014-04-10 다우 글로벌 테크놀로지스 엘엘씨 향상된 열 전도성을 갖는 강성 폴리우레탄 발포체의 성형 방법

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US2761565A (en) 1954-03-19 1956-09-04 Clyde E Hutchinson Filter units
WO2000039497A1 (fr) 1998-12-28 2000-07-06 Shell Internationale Research Maatschappij B.V. Conduites preisolees et leur procede de production
US6627018B1 (en) * 2000-10-17 2003-09-30 Advance Usa, Llc System and method of forming composite structures
DE102009044515A1 (de) * 2008-11-18 2010-05-20 General Electric Co. Membranstruktur für vakuum-unterstütztes Formen faserverstärkten Gegenstandes
US20110260351A1 (en) * 2009-02-20 2011-10-27 Crios S.P.A. Vacuum-assisted foaming method and apparatus for moulding insulation of refrigeration containers
US20120121805A1 (en) * 2010-11-17 2012-05-17 Fomo Products, Inc. Method for filling wall cavities with expanding foam insulation

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"Polyurethan Taschenbuch", 2001, CARL HANSER VERLAG, pages: 83 - 102

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US20150183143A1 (en) 2015-07-02
MX2015001328A (es) 2015-04-08
US9950454B2 (en) 2018-04-24
MX361996B (es) 2018-12-19
EP2879852A1 (fr) 2015-06-10
CN104507656A (zh) 2015-04-08
EP2692501A1 (fr) 2014-02-05
EP2879852B1 (fr) 2020-03-04

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